Iron oxides and oxyhydroxides are commonly of considerable importance in the sorption of ions onto rocks, soils and sediments. They can be the controlling sorptive phases even if they are present in relatively small quantities. In common with other oxides and clay minerals, the sorptionpH-edge of metals is directly linked to their hydrolysis: the higher the residual charge on the metal ion, the lower the pH-edge. Modelling of this process has been successfully carried out using different microscopic or macroscopic definitions of the interface (e.g. surface complexation orion exchange models that may or may not include mineralogical descriptions). The influence of organic material on the sorption of many metals is of significant. This organic material includes simple organic molecules and more complex exopolymeric substances (e.g. humic substances) producedby the decay of natural organic matter. Sorption of this organic material to mineral surfaces has been the subject of a large body of work. The various types of organic substances do not share the same affinities for mineral surfaces in general, and for iron oxides and oxyhydroxides in particular.In those cases in which successful models of the component binary systems (i.e. metal–surface, metal–organic, organic–surface) have been developed, the formation of mixed surface complexes, the evolution of the surface itself, the addition order in laboratory systems, andthe evolution of natural organic matter fractions during sorption, have often precluded a satisfactory description of metal–surface–organic ternary systems over a sufficiently wide range of parameter values (i.e. pH, ionic strength, concentration of humic substances). This manuscriptdescribes the reasons for some successes and failures in the modelling of the ternary systems. Promising recent advances and possible methods of providing more complete descriptions of these intricate systems are also discussed.

Ferric precipitates in the water column at the San Telmo acidic mine pit lake in the Iberian Pyrite Belt, southwest Spain, have been studied by scanning electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, X-ray fluorescence, inductively coupled plasma massspectrometry and other complementary techniques. These Fe(III) precipitates were recovered from sediment traps which were left at different depths (25, 35, 40 and 100 m) in the lake for several months. Seasonal variations in the water chemistry were recorded to link the mineralogical findingsto vertical and temporal changes in aqueous composition. The results indicate that schwertmannite is the first Fe(III) mineral to crystallize after the oxidation of Fe(II), in agreement with previous studies. Schwertmannite is kinetically favoured in comparison to other Fe(III) minerals, andit buffers the pH at 2.6–3.0. It is metastable, and alters to a (H3O+)- and (K+)-bearing jarosite (containing 58 mol.% H3O+ and 42 mol.% K+ on average) at lower pH (e.g. at pH 2.2–2.5 in the summer season), eitherin the water column (during settling) and/or in the benthic sediments, in a time period of weeks to months. The extent of hydronium substitution at the alkali site in the jarosite reflects the higher activity of free aqueous protons in solution (10–2.2 to 10–3.0)in comparison to the activities of K+ (10–4.5) and Na+ (10–3.2). Microscopic examination of mixed schwertmannite–jarosite precipitates found in the water column suggest that some textural and compositional features of metastableschwertmannite (e.g. the internal 'pincushion' arrangement and incorporation of trace amounts of Mg, Al, As and Pb) are conserved in the jarosite during the early stages of the mineralogical transformation, but many of these relics are lost in the later stages of crystal growth. Despite thehydronium-rich nature of the jarosite solid solution, this material is also an important sink for K+, which decreases in concentration with decreasing pH unlike most of the other major cations in the water column (notably Na+, Mg2+, Ca2+, Al3+,Fe3+, Cu2+, Zn2+). In addition to the release of Fe3+ to the aqueous solution, the conversion of schwertmannite to (H3O+, K+)-bearing jarosite consumes protons and thus may represent an additional pH control at SanTelmo and other acidic mine pit lakes of the area.

Approaches currently used for remediating acid mine drainage (chiefly active chemical treatment and passive bioremediation systems) have a number of major detractions, including their failure to recover potentially valuable metals from these waters. Bioremediation strategies that utilizereactor-housed microorganisms can circumvent this problem, but have tended not to be widely used due to their relatively high costs. We have devised innovative approaches for remediating mine waters that use acidophilic bacteria to remove metals either as oxidized or reduced phases, usingmodular bioreactors that are designed to operate at minimal cost and to generate products that have commercial value. A composite system is described that combines microbial oxidation of ferrous iron with abiotic precipitation of ferric iron as schwertmannite, a mineral that has commercialvalue as an absorbent of arsenate and other environmental pollutants, and as a pigment. Sulfidogenic bioreactors maintained at acidic pH values are used to selectively precipitate metal sulfides, such as CuS. Tests with synthetic mine drainage containing mixtures of soluble metals confirmedthat these systems can generate relatively pure mineral deposits from complex acid waters. The units are designed to be configured differently, according to the nature of the mine water requiring treatment.

This study describes geochemical barriers that have developed at three different localities in sulfiderich tailings in the Kemerovo region of Western Siberia, Russia. Iron oxyhydroxides, gypsum, malachite, chalcanthite, goslarite, bianchite, gunningite and copper and zinc chloridescrystallized in the sequence specified at an evaporative barrier around glassy slag produced by the Belovo zinc processing plant. A complex cemented barrier that has developed within the old Salair sulfide tailings contains two well defined layers: an upper layer containing Fe(III) mineralsand gypsum as cements in which Pb, As, Mo, Ni and Co have been deposited; and (2) a lower calcite- and gypsum-bearing layer, in which phases containing Zn, Cd and Cu have been deposited. A complex organic-mineral barrier below the Ursk sulfide tailings consists of peaty organic matter, clayminerals and iron oxyhydroxides cemented by gypsum. Elements that have leached from the tailings are present in this barrier in a variety of different forms: Ca and Mn are present as water-soluble species; Cu, Fe and Zn are present as species produced by interaction with organic matter viaion-exchange, metal humate formation and cation bridging in organic-mineral complexes; Pb and As are co-precipitated with and/or adsorbed onto iron oxyhydroxides; gold has been deposited as minute particles of native metal. The mechanisms for the formation of the different geochemical barriersare discussed.

The capabilities of the asymmetrical flow field-flow fractionation (AsFlFFF) technique coupled with inductively coupled plasma mass spectrometry and UV–Vis spectrophotometry in the characterization of synthetic and natural colloidal samples are demonstrated in two different systems.The first system is a sol of hectorite which was co-precipitated in the presence of Lu. The results show that hectorite nanoparticles can be mobilized from a bulk sample and that they still contain the dopant Lu, which is homogeneously incorporated into the hectorite crystal structure. Thesecond system is a natural groundwater from the Gorleben site on the northern German plain, which is being tentatively explored to assess its suitability as a nuclear waste repository. Colloidal matter heterogeneity is evident in this system. Alkaline-earth elements are mainly found as ionicspecies. Rare earth elements (REEs) and actinides are distributed in two main colloidal fractions: the heavier REEs and U are concentrated in the <4 nm fraction corresponding to the size range of organic colloidal particles, whereas lighter REEs and Th are concentratedin colloidal particles between 4 and 18 nm in size that are both organic and inorganic in nature. Similar results are reported for another sample from the same site, collected ∼2 km from the first one, demonstrating the homogeneity of the aquifer system and/or a possible colloid migrationpathway. The extent of the reversibility of colloid–radionuclide interactions remains to be evaluated.

Hectorite was synthesized from a Eu(III)-bearing brucite precursor in a multistep procedure. In a separate experiment, Eu(III) ions were adsorbed onto hectorite in suspension. Colloids were extracted from both samples. The size distributions in the colloidal fractions were characterizedby application of the asymmetrical flow field-flow fractionation (AsFlFFF) method and the corresponding elemental compositions were obtained by ICP-MS. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to characterize the local chemical environment surrounding Eu in thebulk samples and in the colloidal fractions.

The EXAFS results show that Eu is associated with hectorite upon co-precipitation or adsorption. Results from AsFlFFF suggest that Eu is structurally associated with the colloidal fraction extracted from bulk Eu-bearing co-precipitated hectorite.The AsFlFFF data are different for the colloidal fraction containing Eu(III) adsorbed on hectorite; in this sample they are consistent with a surface retention mechanism. These small but significant differences enable surface sorbed Eu to be distinguished from co-precipitated Eu. Eu is verylikely located in a clay-like environment in the co-precipitation experiment, and it forms inner-sphere surface complexes in the adsorption experiment. The results obtained using the different experimental techniques agree, and show the benefits of using multiple methods of analysis.

Trivalent europium was used as non-radioactive chemical homologue for trivalent actinides. Similar retention mechanisms are expected for the trivalent actinides if they are co-precipitating with or adsorbing onto sheet silicates. The present study provides information which can be usefullyadded to the safety assessments required for deeply buried nuclear waste disposal sites.

Mechanisms for the incorporation of carbonate into minerals of the apatite group have been explored in both the geological and medical literature. An important problem with respect to biological apatite, which requires further clarification, is the hydroxyl content of the carbonatedapatite of bone. Recent studies reveal bone apatite to contain only ∼20 mol.% of the hydroxyl content of stoichiometric hydroxylapatite, with negligible chloride or fluoride. We investigated the hypothesis that the development of vacancies in the hydroxyl channel sites is a charge-balancingmechanism for the substitution of carbonate ions into hydroxylapatite. Raman spectroscopic analyses of synthetic carbonated apatites (containing 1 to >15 wt.% carbonate) show that their hydroxyl ion concentration correlates inversely with carbonate concentration. The specific relationshipbetween carbonate and hydroxyl concentration in these samples closely follows the theoretical relationship defined by type-B substitution of carbonate for phosphate in the apatite structure. However, the 6–8 wt.% carbonate concentration in bone apatite falls far short of accounting forall of the hydroxyl depletion that occurs in bone apatite. Some of the additional hydroxyl depletion in bone apatite might result from substitution of Na+ for Ca2+, but further mechanism(s), perhaps (HPO4)2– substitution, must also play a significantrole.

Whiteite-(CaMnMn), CaMnMn2Al2[PO4]4(OH)2·8H2O, is a new hydrous phosphate of Ca, Mn and Al, which is closely related to both jahnsite-(CaMnMn) and the minerals of the whiteite group. It is monoclinic, P2/a, with a = 15.02(2), b = 6.95(1), c =10.13(3) Å, β = 111.6(1)°, V = 983.3(6) Å3, Z = 2 (from powder diffraction data) or a = 15.020(5), b = 6.959(2), c = 10.237(3) Å, β = 111.740(4)°,V = 984.3(5) Å3, Z = 2 (from single-crystal diffraction data). The mineral was found in the Hagendorf Süd granitic pegmatite (Germany) as small (up to 0.5 mm in size) crystals elongated on a and tabular on {010}. The crystals are either simply or polysyntheticallytwinned on {001}. They crystallize on the walls of voids within altered zwieselite crystals or form coronas (up to 1 mm in diameter) around cubic crystals of uraninite. The mineral is transparent, colourless to pale yellow (depending on Al–Fe3+ substitution), with a vitreouslustre and a white streak. The cleavage is perfect on {001}, the fracture is stepped and the Mohs hardness is 3½. In transmitted light, the mineral is colourless; dispersion was not observed. Whiteite-(CaMnMn) is biaxial (+), α = 1.589(2), β = 1.592(2), γ = 1.601(2)(589 nm), 2Vmeas = 60(10)°, 2Vcalc = 60.3°. The optical orientation is X = b, Z^a = 5°. The calculated and measured densities are D calc = 2.768 and D meas = 2.70(3) g cm–3, respectively.The mean chemical composition determined by electron microprobe is Na2O 0.53, MgO 0.88, Al2O3 11.66, P2O5 34.58, CaO 4.29, MnO 17.32, FeO 8.32, ZnO 2.60 wt.%, with H2O 19.50 wt.% (determined by the Penfield method), giving atotal of 99.68 wt.%. The empirical formula calculated on the basis of four phosphorus atoms per formula unit, with ferric iron calculated to maintain charge balance, is (Ca0.63Zn0.26Na0.14)Σ1.03(Mn0.60Fe0.40 2+)Σ1.00(Mn1.40Fe0.37 2+Mg0.18Fe0.06 3+)Σ2.01(Al1.88Fe0.12 3+)Σ2.00[PO4]4(OH)2·7.89H2O.The simplified formula is CaMnMn2Al2[PO4]4(OH)2·8H2O. The mineral is easily soluble in 10% HCl at room temperature. The strongest X-ray powder-diffraction lines [listed as d in Å (I) (hkl)]are as follows: 9.443(65)(001), 5.596(25)(011), 4.929(80)(210), 4.719(47)(002), 3.494(46)(400), 2.7958(100)(022). The crystal structure of whiteite-(CaMnMn) was refined for a single crystal twinned on (001) to R 1 = 0.068 on the basis of 5702 unique observed reflections. Itis similar to the structures of other members of the whiteite group. The mineral is named for the chemical composition, in accordance with whiteite-group nomenclature.

The new minerals d'ansite-(Mn), Na21Mn2+(SO4)10Cl3, and d'ansite-(Fe), Na21Fe2+(SO4)10Cl3, occur as encrustations in fumaroles at Vesuvius, Naples, Italy and La Fossa crater,Vulcano, Aeolian Islands, Italy, respectively. Both minerals are cubic and crystallize in space group I 3d. D'ansite-(Mn) forms colourless translucent tristetrahedral crystals up to 0.2 mm on edge; d'ansite-(Fe) forms aggregates of colourless to white complex isometriccrystals of about the same size. Chemical analyses obtained by energy-dispersive spectrometry on an electron microprobe gave the following mean compositions: d'ansite-(Mn), Na2O 39.37, MnO 3.46, MgO 0.13, SO3 49.99, Cl 6.36, O=Cl–1.44, total 97.87 wt.%, correspondingto an empirical formula, on the basis of 43 anions, of Na20.61 (Mn2+ 0.79Mg0.05)Σ0.84S10.13O40.09Cl2.91; and d'ansite-(Fe), Na2O 39.12, FeO 4.18, MgO 0.12, SO3 49.91, Cl 6.81,O=Cl –1.54, total 98.60 wt.%, corresponding to an empirical formula of Na20.42(Fe2+ 0.94Mg0.05)Σ0.99S10.08O39.89Cl3.11. The six strongest reflections in the X-ray powder diffraction pattern ofd'ansite-(Fe) [listed as dobs(Å) (I) (hkl)] are as follows: 2.807(100)(044), 2.570(37)(235), 1.714(29)(129), 3.384(27)(233), 3.113(26)(134), 2.108(15)(237). The unit-cell parameters obtained from single-crystal data are 15.9291(9) and 15.882(3) Åfor d'ansite-(Mn) and d'ansite-(Fe), respectively. The structure of both minerals was refined, using single-crystal diffraction data, to final R parameters of 0.0309 and 0.0336 on reflections with I > 2σ(I). The structure contains three independent Na sites, oneof which is partially occupied by Mn2+ or Fe2+, two independent sulfate anions and one chlorine site.

This study reports the discovery of inclusions, which are inferred to represent trapped primary silicate gels, in simple pegmatites genetically connected to the Precambrian Rønne granite of Bornholm Island, Denmark. These inclusions are randomly associated with more typical meltand alkali-carbonate-rich and bicarbonate-rich fluid inclusions. Their relationship to the latter and to the formation of the pegmatite bodies is discussed. The silicate gel inclusions become increasingly common towards the quartz cores of the pegmatites, and are considered to demonstrateincreasing water and alkali carbonate concentrations in the pegmatite-forming liquid, and an accompanying tendency for sol/gel formation. This discovery may have important implications for the formation of the quartz cores of pegmatites. The possible origin of the alkali-carbonate concentrations in pegmatite-forming fluids is also briefly discussed.

Calciodelrioite, ideally Ca(VO3)2(H2O)4, is a new mineral (IMA 2012-031) from the uraniumvanadium deposits of the eastern Colorado Plateau in the USA. The type locality is the West Sunday mine, Slick Rock district, San Miguel County, Colorado.The new mineral occurs on fracture surfaces in corvusite- and montroseite-impregnated sandstone and forms as a result of the oxidative alteration of these phases. At the West Sunday mine, calciodelrioite is associated with celestine, gypsum, huemulite, metarossite, pascoite and rossite. Themineral occurs as transparent colourless needles, bundles of tan to brown needles and star bursts of nearly black broad blades composed of tightly intergrown needles. Crystals are elongate and striated parallel to [100], exhibiting the prismatic forms {001} and {011} and having terminationspossibly composed of the forms {100} and {61}. The mineral is transparent and has a white streak, subadamantine lustre, Mohs hardness of about 2½, brittle tenacity, irregular to splintery fracture, one perfect cleavage on {001} and possibly one or more additional cleavages parallel to [100].Calciodelrioite is soluble in water. The calculated density is 2.451 g cm– 3. It is optically biaxial (+) with α = 1.733(3), β = 1.775(3), γ = 1.825(3) (white light), 2Vmeas = 87.3(9)° and 2Vcalc = 87°. The optical orientationis X = b; Z ≈ a. No pleochroism was observed. Electronmicroprobe analyses of two calciodelrioite samples and type delrioite provided the empirical formulae (Ca0.88Sr0.07Na0.04K0.01)Σ1.00(V1.00O3)2(H2.01O)4,(Ca0.76Sr0.21Na0.01)Σ0.98(V1.00O3)2(H2.01O)4 and (Sr0.67Ca0.32)Σ0.99(V1.00O3)2(H2.00O)4, respectively.Calciodelrioite is monoclinic, I2/a, with unit-cell parameters a = 14.6389(10), b = 6.9591(4), c = 17.052(2) Å, β = 102.568(9)°, V = 1695.5(3) Å3 and Z = 8. The seven strongest lines in the X-ray powder diffractionpattern [listed as dobs Å (I)(hkl)] are as follows: 6.450(100)(011); 4.350(16)(013); 3.489(18)(020); 3.215(17)(022); 3.027(50)(multiple); 2.560(28)(15,413); 1.786(18)(028). In the structure of calciodelrioite (refined to R1 = 3.14% for1216 Fo > 4σF), V5+O5 polyhedra link by sharing edges to form a zigzag divanadate [VO3] chain along a, similar to that in the structure of rossite. The chains are linked via bonds to Ca atoms, which also bond to H2Ogroups, yielding CaO3(H2O)6 polyhedra. The Ca polyhedra form a chain along b. Each of the two symmetrically independent VO5 polyhedra has two short vanadyl bonds and three long equatorial bonds. Calciodelrioite and delrioite are isostructuraland are the endmembers of the series Ca(VO3)2(H2O)4–Sr(VO3)2(H2O)4. Calciodelrioite is dimorphous with rossite, which has a similar structure; however, the smaller 8-coordinate Ca site in rossitedoes not accommodate Sr.

The crystal structure of kraisslite, orthorhombic (pseudo-hexagonal), a = 8.1821(1), b = 14.1946(3), c = 43.9103(8) Å, V = 5099.8(2) Å3, Z = 4 and d calc = 4.083 g cm–3, has been solved bydirect methods and refined in the space group C2221 to an R 1 index of 1.68% for 7432 observed (|F o| > 4σ|F|) reflections. Electron-microprobe analysis gave the following chemical composition: As2O510.86,As2O36.18, SiO213.39, Al2O30.25, Fe2O32.06, MnO 51.14, ZnO 7.39, MgO 2.13, CaO 0.05, H2Ocalc = 4.50, sum 97.95 wt.%; and empirical formula: Zn2.91(Mn23.07Mg1.69Ca0.03)Σ=24.79(Fe0.83 3+Al0.16)Σ=0.99(As3+O3)2[(Si0.71As0.30 5+)O4]10(OH)16 calculated on the basis of 62 anions with (OH) = 16 and As3+/(As3++ As5+) taken from the refined crystal structure. The general formula, [4]Zn3(Mn,Mg)25(Fe3+,Al)(As3+O3)2[(Si,As5+)O4]10(OH)16, differs from those given previously.

There is one As3+ site with a <As–O> distance of 1.780 Å and a stereochemistry typical of a stereoactive lone-pair of electrons. There are five tetrahedrally coordinated T sites with <T–O> distances from 1.635 to 1.692 Å; the T(1)site is fully occupied by As5+, and the T(2)–T(5) sites are occupied by both Si and As5+. There are two tetrahedrally coordinated Zn sites with <T–O> distances of ∼1.996 Å, both of which are occupied by dominantZn and minor Mn2+. There are thirteen octahedrally coordinated M sites, twelve of which are occupied by dominant Mn2+ with lesser Mg and minor Zn; <M–O> distances are in the range 2.197–2.284 Å. The <M(13)–O> distanceis 2.083 Å and its lower site scattering indicates occupancy by Fe3+, Mn2+, Mg and Al. The structure consists of five crystallographically distinct layers of polyhedra, labelled m = 0 – 4. Layer m = 0 consists of corner-sharing Zn and (Si, As5+)tetrahedra, and layers m = 1–4 each consist of trimers of Mn2+ octahedra linked by (Si, As5+) tetrahedra and intrasheet hydrogen bonds (m = 1, 3) or (Si, As5+) tetrahedra and (Fe3+,Al) octahedra (m = 2) or (As5+)tetrahedra and (As3+O3) triangular pyramids and intrasheet hydrogen bonds (m = 4). The layers stack along [001] with reversals of the sequence m = 1, 2, 3, 4 at z = 0, ¼, ½ and ¾. Kraisslite is a member of the mcgovernite family.

The crystal structure of deliensite, Fe[(UO2)2(SO4)2(OH)2](H2O)7, was solved by direct methods and refined to R 1 = 6.24% for 5211 unique observed reflections [I obs > 3σ(I)],on a crystal that was found to consist of rotational and inversion (merohedral) twins, from Jeroným mine, Abertamy in the Czech Republic. The presence of four twin domains was taken into account in the refinement. The structure is orthorhombic, space group Pnn2, with unit-cellparameters a = 15.8514(9), b = 16.2478(7), c = 6.8943(3) Å, V = 1775.6(1) Å3 and Z = 4. The crystal structure of deliensite contains uranyl-sulfate sheets with a phosphuranylite topology, consisting of dimers of edge-sharing uranylpentagonal bipyramids linked by corner-sharing with sulfate tetrahedra. The sheets lie in the (100) plane and are decorated by [Fe2+O(H2O)5] octahedra; two weakly bonded H2O molecules are present in the interlayer. The [Fe2+O(H2O)5]octahedron is linked directly to the sheet via the uranyl oxygen atom. Adjacent sheets are linked by hydrogen bonds only. The sheet topology and geometrical isomerism is discussed and a comparison of the composition obtained from electron-probe microanalysis, powder-diffraction data, Ramanand infrared spectra of deliensite samples from Mas d'Alary, Lodève, France; L'Ecarpière mine, Gétigné, France; and several localities at Jáchymov, Western Bohemia, Czech Republic is made.